CS244431B2 - Herbicide or fungicide and method of its efficient substance production - Google Patents

Abstract

Compounds of the general formula: <CHEM> in which R<1> represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R<2> represents a hydrogen atom, a methyl or a methoxy group; Ar represents an optionally substituted phenyl group or an optionally substituted heteroaromatic ring containing 1 or 2 oxygen, sulphur and/nitrogen atoms; each of X and Y independently represents a hydrogen or halogen atom or an alkyl, haloalkyl or alkoxy group; and one of A and B represents a group -CO-; -CR<3>(OR<4>)- or -CR<3>(SR<4>), in which R<3> represents a hydrogen atom or an alkyl group and R<4> represents a hydrogen atom, an alkyl, alkenyl, alkynyl or cycloalkyl group, an optionally substituted phenyl or benzyl group, or an acyl group derived from a carboxylic, sulphonic or phosphoric acid; -C(OR<5>)(OR<6>)-, -C(OR<5>)(SR<6>)- or -C(SR<5>)(SR<6>)-, in which each of R<5> and R<6> independently represents an alkyl group or together represent an alkylene group; -CH(CH2COOR<7>)- in which R<7> represents an alkyl group; or -(CNR<8>)- in which R<8> represents a group OR<4> or NHR<4>; and the other of A and B represents a group -CR<9>R<1><1>-CR<1><0>R<1><2>-, in which each of R<9>, R<1><0>, R<1><1> and R<1><2> independently represents a hydrogen atom or an alkyl group or R<1><1> and R<1><2> together represent a carbon-carbon bond, a -CH2- group or an oxygen atom exhibit herbicidal and fungicidal properties.

Description

(54) A herbicidal and / or fungicidal composition and a process for the manufacture of an active ingredient thereof

A herbicidal and / or fungicidal composition comprising, together with a carrier, the active compound phenylurea of the formula I

X

(X) wherein the two R c groups together represent an alkylene group containing up to 4 carbon atoms, and the other of the substituents A and V represents an ethylene * 1,2-epoxyethylene, vinylene or 1,2-cyclopropylene group. The active ingredient of the herbicidal and / or fungicidal composition according to the invention is obtained by reacting an aniline of the general formula (XI):

R _<P and R each independently represent a ^{C 1} hydrogen or methyl,

X represents a hydrogen atom,

Y represents a hydrogen or chlorine atom,

Ar is pyridyl or phenyl, which is optionally further substituted, one substituent А а В represents = C0 = CH _(ORa) or »CH _(SR), in which ^{4 4}

R represents a hydrogen atom, an alkyl group ^{of 4} β 1 to 4 carbon atoms, arylcarbonyl Fe- or benzyl group, or an alkanoyl or alkylsulfonyl, wherein the alkyl portion contains 1 to 4 carbon atoms or a group of formula = (C (OR ₅₎ (OR ₅ ) or * C (SR ₅ ) (SR ₅ ),

X

Y wherein the substituents are as defined above, with phosgene and an amine or alkylcarbamoyl chloride.

The present invention relates to a herbicidal and / or fungicidal composition which contains urea derivatives not yet described as active ingredient. The invention also relates to a method of active ingredient of the herbicidal and / or fungicidal composition.

The prior art is evident from U.S. Patent No. 2,655,447, which discloses a very broad class of urea derivatives having herbicidal properties. More than twenty-five lats have elapsed since the discovery of this class of compounds, during which a number of new types of Properties!. The present inventors have now discovered a new class of urea derivatives having interesting herbicidal properties and in some cases also having fungicidal properties.

The invention therefore relates to a herbicidal and / or fungicidal composition which, together with the carrier, contains the phenylurea of the formula I as active ingredient.

X

^Я 2 (I) • kd.

R | and ^R2 independently represent a hydrogen atom or a methyl group,

X represents a hydrogen atom,

Y represents a hydrogen atom or a chlorine atom,

Ar represents a pyridyl group or a phenyl group which are optionally substituted by a chlorine or fluorine atom, a methyl group, a trifluoromethyl group or a methoxy group, one of which is represented by the formula CCO, skupinu (ΟΗ) or ³ CH (SR _4). ) in which

R is hydrogen, alkyl of 1 to 4 carbon atoms, phenyl, benzyl, or alkanoyl or alkylsulfonyl wherein the alkyl moiety contains one to four Atoa atoms or is R ³ C (OR ^) (OR ^) or CC (SRj) (SR SR), wherein the two R dohromady groups together represent an alkylene group containing up to 4 carbon atoms, and the other of the substituents а and představuje represents an ethylene group, a 1,2-epoxy ethylene group, a vinylene group, or 1; , 2-cyclopropylene group ·

Unless otherwise indicated, all alkyl groups and alkyl moieties of other groups contain up to 4 carbon atoms throughout the invention.

In a particularly preferred embodiment of the invention R1 represents a hydrogen atom.

Particularly preferred ^R ₂ is methyl.

The phenyl group Ar may be substituted with one or more substituents commonly found on the aromatic ring. Particularly preferred such substituents are chlorine or fluorine, methyl or trifluoromethyl. In a particularly preferred embodiment of the invention, the phenyl group is unsubstituted or substituted by one or two substituents. Chlorine is a particularly preferred substituent.

the pyridyl group may be substituted by one or more of the preferred substituents listed above and the phenyl group Ar. Particularly preferred substituents are chlorine, fluorine and methyl. In the most preferred embodiment of the invention, the pyridyl group is unsubstituted.

In a preferred embodiment of the invention, the substituent R 1 is a hydrogen atom, a C 1 -C 4 alkyl group, for example a metal group, an ethyl group or an isopropyl group, a benzyl group, and a methysulfonyl group.

In a preferred embodiment of the invention, one of A and B, in particular A, is -CO, -CH (OR) - or -CH (ISR) -, optionally -C (OR) (OR) -isSo -C (SR) (SR) -, wherein R 1 and R 8 have the same meanings as given above with respect to these groups. Particularly preferred groups are -CO, -CH (OH) -, -CH (OCR) and

/ ° ^H 2

X i

OCR

In a preferred embodiment of the present invention, the second of tubstitusites A and B, particularly preferably jubstitueite B, is a group of the formula -CH 2 CH- or -CR-CR-.

The group B is preferably attached to the phenyl ring in the para position, in a particularly preferred embodiment it is attached to the phenyl ring in the meta position, in view of the purification of the group -HR-.

In the various moieties present in moieties, the compounds of the invention may be in the form of geomeeric and / or optical isomers. Included within the scope of the present invention are all the individual isomers and some of these isomers, particularly mixtures of regioisomeric pairs in which the A and B tubstituents are interchangeable.

The present invention also provides a process for the preparation of an active ingredient for a herbicidal and / or fungicidal composition. This method comprises reacting a compound of formula (II) wherein

Y (II)

Ar, Α, Β, X and X mm, or the meaning of Formula I, are either

(a) compound of the pattern IV

C1-CON (CR) R where

R is as defined for formula I, or is

(b) phosgene and amine of formula III (IV)

CRNHR III

244431 4 where

Rg is as defined for formula (I).

The compound obtained is optionally converted into another compound of the formula I by further known reactions, where the meanings of the substituents correspond to the meanings given in the general formula I or their preferred low-molecular-wavelengths.

Both of the above-mentioned alternative reactions are chemically completely elective because phosgene in situ reacts with the amine to form alkylsulfonate.

The above process (a) can be carried out with or without a solvent. Suitable solvents include hydrocarbons and halogenated hydrocarbons, such as benzene, toluene or carbon tetrachloride. In a preferred embodiment, the process is carried out essentially under anhydrous substances. Since it is a condensation reaction in which hydrogen chloride is eliminated, it is possible to work in the presence of a dehydroechlorinating agent. Organic or basic compounds may be advantageously used as such, and it has been found that, in the absence of a solvent, it is preferred to use sodium acetate, while in the presence of a solvent, it is preferable to use organic basic compounds such as triethylamine or pyridine. When suitably performed either reaction is carried out at a temperature from 0 to 80 ° C, price <m ^{Z without} them operating at t e ^p room lots and after ^the rea tion mixture can reaktaí processed by conventional methods.

The above method b) is preferably carried out in the presence of a solvent, for example in the present case ^tL oíodíkov ^Star it extended ^ ijdš & Ha as toluene, at ^t ep ^L ot ^y in the range from ⁸⁰ to ¹²⁰ ° C, and normally is carried out at reflux temperature If necessary, the isocyanate formed as the intermediate can be isolated from the reaction mixture, but preferably the reaction mixture is reacted in situ with an amine of the formula IV. This reaction is above odně prov ^h ^ i ^ for the Otto ^{0 and 30} ° ^C but lejčastěti operating at temperatures mísitnori. The desired product can be isolated from the reaction mixture by any suitable means.

Extract fabric for the process. According to the invention, the compounds of formula IX are novel compounds. These compounds of general formula II can be reduced by reducing the compound of formula V

AND

Ar - A - B - i - || (V) where

Ar, A + Β, I and I have the meanings given for the lunch formula I.

In this case, any suitable reducing agent, for example hydrogen gas in the presence of the catalyst, such as based on platinum, nickel or nickel, may be used, or a hydride, such as a suction metal hydride, e.g.

The group = CO forming A or B can be converted to another by a method analogous to the generally known method? To form other possible groups A or B. Typical methods are, for example:

Reaction of a ketone with a suitable alcohol or thiolam, or derivatives thereof. This reaction is usually carried out under acidic conditions.

2. Reduction of the ketone using a suitable reducing agent. such suitable agents include hybrids, for example, metal cobalt metal hydrides, for example, sodium borohydride or lithium aluminum hydride.

3 * Reaction of a ketone with a Grignard reagent of formula

R ³ H ⁸ Hal, wherein alkyl represents a

Hal represents a halogen atom, in particular a bromine atom,

4. Reaction of alcohol with hydrogen sulphide in the presence of acid catalyst ·

Alkylation of an alcohol or thiol using a suitable alkylating agent, for example an alcohol or thiol in the presence of an acid catalyst to form the corresponding alkyl ester or thioester, followed by reaction of said alcohol or thiol with the corresponding reagent to form another ether.

Esterification of alcohol or thiol using an esterifying agent.

As mentioned above, the resulting compound of formula (I) may be converted to any other suitable desired compound of formula (I). For example, a compound of formula (I) may be alkylated by reaction with a suitable alkylating agent such as an alkyl halide; an alkyl iodide, to form a compound of formula (I) wherein R 1 represents an alkyl group having a total of 1 to 4 carbon atoms. Further, the groups A and V in the resulting urea compound can be converted to other A and V groups by methods analogous to those described above for the preparation of intermediates of compounds XI or V. For example, if desired the preparation of a compound of formula I in which A is -CH (OH) - may be accomplished by reduction of keto group A either in a compound of formula I or in a prodrug of compounds of formula IX or V.

The compounds of the present invention exhibit herbicidal properties and in some cases also fungicidal properties. The present invention therefore also relates to herbicidal and / or fungicidal compositions comprising a compound of formula I together with a carrier material. The invention also encompasses within its scope a method of controlling the growth of fungi and / or undesirable plants at a designated site by administering at said designated site a compound of the invention or a composition of the invention. The designated location may be, for example, the area under which crop plants are grown, for example plants or seeds of such crop plants, such as cereals or soybeans, are present. For example, the dosage amount of active ingredient may range from 0.05 to 4 kg / ha ·

When the compounds of the invention or the compositions of the invention are used as herbicides, the treatment is preferably carried out post-emergence. When a compound of the invention or composition of the invention is used as a fungicidal agent, the treatment may be carried out in an appropriate manner on plants, seeds or soil.

The carrier material of the compositions of the present invention may be any suitable material with which the active ingredient is mixed to facilitate the application of the compositions at the intended site to be treated, or to facilitate storage, transport or handling. The carrier may be a solid or a liquid, including substances which are normally in a gaseous state but which have been compressed to a liquid form, and any carrier that is commonly used in the preparation of agricultural compositions may be used. Preferably, the compositions contain the active ingredient in an amount ranging from 0.5% to 95% by weight.

Suitable solid carriers are natural and aesthetic clays and silicates such as natural silica such as diatomaceous earth; topical silicates such as maatek; magnesium silicates, such as attapulgites and vendculites; aluminum silicates such as kaolinite, iontolonates and mica; furthermore calcium carbonate, calcium sulfate, amorate sulfate; aesthetic. hydrated silicas and synthetic calcium silicate or synthetic silicate; elements such as aubergine and sulfur; natural and synthetic polymers such as coumarone resins, polyrinyl vinyl chloride, and styrene polymers and copolymers, solid polymorphs; bitumen waxes such as beeswax, paraffin wax, and chlorinated waxing; and finally solid hinoiva such as suppephosphates.

Suitable liquid carriers include, in the compositions of the invention, water, alcohols such as isopropanol and glytals; ketones, such as acetone, methyl, methyl, ethyl ketone and cyclohexanone; other ethers; aromatic or α-aliphatic hydrocarbons such as benzene, toluene and. : xylene; petroleum fractions, such as gasoline n light mineral oils; and chlorinated hydrocarbons such as cH, carbon tetrachloride, percarbonate and trichloroethane. it is often convenient to use mixtures of different liquid carriers.

Agricultural compositions are often prepared and transported in concentrated form, which is subsequently diluted prior to use by the user. Gloom ^ m ^ <^ i ^ min ^ IT small your nositavé ^{substance is enhanced,} wherein ^a surfactant is also inideш ⁿ ·! Naréaě tent.o process rozřetavtoí tančentrované mold. Therefore, it is desirable that at ^least one carrier in the composition of the present invention is a surfactant. For example, the composition of the present invention may comprise at least two carriers, at least one of which is a surfactant.

The surfactant may be an emulsifying agent, a dispersing agent or a wetting agent, and may be nonionic or ionic. Examples of suitable surfactants include sodium or calcium salts of polyacrylic acids and ligninsullanic acids; does further koulenza & II products of fatty acid amide or allfailklýteh amines or amides ззЛи ^ ^ ^ ¹ с a1es ^C o ^{N 12} UH ^- .ítavýc ^H atoms оо ^ & Ь е · ethylene oxide and / or prlpylβnoxidem; fatty acid esters of glycine, sorbitan, sucrose or pentaeirritol; condensates thereof with ethylene oxide and / or hem; furthermore, condensation products of fatty alcohols or alkyl phenols, such as, for example, ethyl esters; or p-1-alkylflaol, with ethylene oxide and / or propylene oxide; Sulphates or those of these condensation products; furthermore an alkali metal salt or an alkaline earth metal salt, preferably a sodium salt, sulfuric acid esters or sulphonates having at least 10 carbon atoms in the ω-γ-γ, for example sodium lauryl, secondary α-ω-sulphate. sodium, sodium sulphonated castor oil, and sodium trisulphosulphonates such as sodium dodecylbenzene phosphate; and polymers of ethyleaoxide, and copolymers of 1-ethylene oxide and pyrimidine.

For example, the compositions of the present invention can be prepared in the form of powdered powders, dusts, grandiose, solutions, emulsion concentrates, leather, concentrate suspensions and aerosols. Typically, the powders usually stand up! active substance. at least 25%, 50%, or 75%, by weight, and usually contain these compositions. in addition to the solid inert carrier material, a stabilizer or substances in the range of from 3 to 10% by weight and / or other additives such as penetrants or levers. Dusts are generally prepared in the form of dusted concentrates having a composition similar to that of a wettable powder, but without a dispersing agent, which are diluted at the site of application with another solid carrier material to form a composition which usually contains the active ingredient in a min. St! ranging from 0.5 to 10% ^ отщеп ^! The granules are generally prepared in such a way that they range in size from 1.676 to 0.152 millimeters, which granules can be prepared by agglomeration or impregnation processes. In general, these granules contain an active ingredient in the range of from 0.5% to 75% by weight, and further an additive in the range of 0 to 10% by weight, which additive may be a surfactant stabilizer. a mole-modifying agent, and a binder. The so-called dry liquid powders consist of relatively small granules having a relatively high concentration of active ingredient. Typically, the volatile cesorates contain, in addition to the solvent and, if necessary, the active ingredient in an amount ranging from 10% to 50% by weight of the two compositions, an emulsifying agent in an amount of from 2 to 20% by weight, in both media. in amounts ranging from 0 to 20% by weight of the two compositions, but may also be a stabilizing agent, a penetration agent and a corrosion inhibitor.

The suspending toners are usually formulated to form a stable, sedimenting, liquid product, wherein the formulations typically contain the active ingredient in an amount ranging from 10 to 75% by weight, a dispersant in the mass in a mat of 0.5 to 15% by weight. a suspending agent in the range of from about 0.1% to about 10% by weight of said suspending agent may be a preservative or an isotropic agent, and may further contain from about 0% to about 10% by weight of other additives such as, for example, ^or n ⁱ dla prevents the rotation of the rotation! Additives .oM ^ ^ ^ ^k srsze ^LIO, TTAB ⁱ L ^{i and} TSRs of ^{y, p} and enetranty littered, and water or an organic chap ей well, in which the active ingredient in the soil Tata insoluble, with certain organic solids or inorganic They may be dissolved in said composition to assist in preventing sedimentation or as anti-lubrication agents in the event of water.

Aqueous dispersion and emulsions, for example, compositions obtained by diluting the powder or the endorate of the present invention with water, are also within the scope of the present invention. These emulsions may be of the water-in-oil or of the oil-in-water type, and may also have a solid vald of consistency.

The compositions of the present invention may also contain other ingredients, such as other compounds which render the herbicidal, insecticidal or fungicidal properties of the invention.

The following examples illustrate the invention. The identity of the compounds obtained was confirmed by NMR and mass analysis and, where possible, melting point.

Example 1

Wíprava ¹ - / oitrof G-EO-A ³ - (^ с Ч-ггГ ο Ι ^ ^- -Pop / - ^ ^^ ο οοu.

According to this example, a solution of 3 / nitrbbenzaphthaldehyde (13.7 grams, 0.1 mole) and 4% nitro-benzophene (in 15.45 grams corresponding to 0.1 mole) in absolute β 2 is used. The mixture is cooled in an ice bath, then saturated with hydrogen chloride gas and then left to stand overnight. The crystalline product obtained is then filtered off and recrystallized from acetone. 21 g of the expected product are obtained, which corresponds to a yield of 73%. Temperature ttoí obtained ^p R ^d is 1Uttu ^ olhrbujle between Π1 to 112 ° C.

Example 2 ·

Preparation ² - (4) (C ¹ -phenyl) -2- ( ² -33-nonsphenolyrene-Chlorine) -1,3-dSosole.

A mixture of the compound of Example 1 (5.8 g, corresponding to 0.02 molar, ethyl acetate (20 ml) and p-toluenesulfonic acid (in a range of 0, 20 ml) was added. 6 grams) in toluene (300 ml) was heated at reflux overnight, and then the water was removed in a water trap and the solution was washed with a saturated acidic solution. The product thus obtained in 6.5 g (97% yield) was used for the next reaction without further purification.

244431 8

Example 3

Preparation of 1- (3-nitrophenyl) -3- (4-chlorophenyl) -3-hydroxyprop-1-em

To a solution of the compound of Example 1 in 8 g equivalent to 0.028 moles in tetrahydrofuran (200 ml) on an ice bath, a solution of 6.8 g of CeCl3 in water (10 ml) is added. the solution obtained is diluted with methanol (75 ml), then slowly treated with sodium borohydride (1.06 g, equivalent to 0.028 mol). After 1 hour, the mixture is acidified with acetic acid, evaporated to a small volume, diluted methylene chloride, washed with saturated sodium bicarbonate and water, then dried and evaporated. Flash chromatography using an alkyl alcohol yielded 7.25 grams of product, corresponding to a 90% yield.

Example 4

Preparation of 1- (3-nitrophenyl) -3- (4-chlorophenyl) -3-methoxy-prop-1-ene

5 g (0.017 mol), silver (4.4 g) and methyl iodide (20 ml) were stirred over aoc. The mixture was then filtered and the filtrate obtained. se. Evaporation after chromatography gave 4.5 g (86%) of methyl ether.

Example 5

Preparation of 1- [3- (4-Chlorobenzoyl) cyclopropane] -2- (4-chlorobenzoyl).

Sodium hydride mixture of 0.9 g of a 50% dispersion, corresponding to 0.18 mol, and trimethylsulfoxonium iodide, 4.3 g, corresponding to 0.018 mol, were stirred in dimethylsulphoxide at 25 ° C at 0 °. C under nitrogen until hydrogen evolution ceased. Then a solution of Example 1 (5 g), equivalent to 0.017 mol, in 50% tetrahydrofuran, and dimethyl sulfoxide (20 ml) were added, after 5 minutes the ice bath was removed. The mixture is then poured into water, extracted with diethyl ether, and the organic extracts are washed several times with water, then dried and evaporated. Chromatography yields 3.8 g of cyclopropane, giving a 76% yield. yield ·

Example

Preparation of 1- (3-Aminophenyl) -3- (4-chlorophenyl) -prop-1-β-Zinc.

To this stirred mixture of the compound prepared according to Example 1 in an amount of 2.9 grams corresponding to 0.01 mole and 5% palladium on charcoal as a catalyst in an amount of 0.3 grams in ethanol at 200 milliliters at 50 ml of a 10% strength aqueous sodium phosphate solution is added at room temperature. The mixture is then stirred until no starting material is heated, as determined by thin layer chromatography (about two hours). The mixture is then filtered using Celite (trade name) and further diluted with methylene chloride to separate the organic layer and the aqueous layer. After separation, the organic layer is washed with water, dried and evaporated to leave the desired compound which then purified by flash chromatography. 2.3 g of product are obtained, corresponding to a yield of 89%.

Example 7

Preparation of 1- / 3-ад1по: Гепу1 / -3- (4-сЬ1огее1уг1 / -ргорад-3-опи).

A suspension of the compound of Example 1 in a quantity of 2.9 grams corresponding to 0.01 mole and 5% platinum on charcoal of 0.3 grams, in ethanol in a volume of 150 milliliters, is hydrogenated in Parrova. Cydrogenic ape-ature until hydrogen consumption ceases. Thereafter, the mixture is filtered and embedded in Celite (trade name), the filtrate thus obtained is filtered off and the desired product remains in approximately quantitative yield.

Examples 8 to 22

Other compounds of formula (II) are executed by a process analogous to that of Examples 6 and 7. Details are given in the table below.

Table I

Example # Ar AND (B) X Y Position B relative to 8 (-chlorophenyl) ^Ď -CH = CH- H H m 9 phenyl -CH (OH) - -CH = CH- H H m 10 phenyl -CHÍOCH) - -CH = CH- H H m 11 phenyl 1_________________1 -CH = CH- H H and 12 4-Chlorophenyl 0% 1_________________1 4OH2CH ₂ 4 H H m 13 4-Cdorfenyl -what- -CH2CH24 H H P 14 (-amino-phenyl) -WHAT- -CH2CH24 H H m 15 Dec 4-cC ^ L ^^^ e ^^^ L -CMCC ^) - -CH2CH24 H H m 16 3,44dtcClooΓenyl -CHCOC ^) - -CH2CH24 H H n 17 (-chlorophenyl) -WHAT- -CH-CH- / CH ₂ H H m 18 ЗЛ-а ^ МюГ enyl & -CH ₂ CH ₂ - H H m 19 Dec phenyl -CHfOC ^) - -CH ₂ CH ₂ - H H rn 20 May phenyl -WHAT- -CH ₂ CH ₂ - H H m 21 phenyl Ď -CH2CH2- H H m 22nd 4-Methyl-phenyl -WHAT- -CH2CH24 H H m

Example 23

Preparation of 1- [3- (3- (4-Chloro-phenyl) -3-oxo-prop-1-enyl) -phenyl] -3,3-dimethyl-urea.

In this example, the compound obtained in Example 6 at 2.0 grams corresponding to 0.006 moles was added to a saturated solution of phosgene in toluene at 100 milliliters. The mixture was then heated at reflux for 30 minutes. Nitrogen is bubbled through the mixture until all excess phosgene has been removed. The solution thus obtained is then cooled to room temperature and treated with 2 ml of dimethylanine. 2.0 g of product are obtained, corresponding to a yield of 93%. Melting point: 159-160 ° C.

Elemental analysis: C Η N

Calculated 64.6 5.6 7.5

Found: 64.5 5.6 7.5

Example 24

Preparation of 1- [3- (3- (4-Chlorophenyl) -3-oxopropyl) phenyl-3,3-dimethylurea].

Following the same procedure as in Example 23, the compound was prepared from the compound of Example 7. The molecular weight of the compound obtained was 330.5 (ascertained by mass spectrometer).

Elementary analysis:

Calculated

65.4 5.7 8.5

Found

65.7 5.7 8.7

Example 25

Preparation of 1- [3- (3- (4-Chloro-phenyl) -3-hydroxy-propyl) -phenyl] -3,3-dimethyl-urea.

In this example, a solution of the compound of Example 24 is added in an amount

6.0 g (0.018 mol) in 200 ml of methanol cooled in an ice bath was treated with 0.66 g (0.018 mol) of sodium borohydride and then stirred for 1 hour. This solution was then acidified with acetic acid, evaporated to a small volume, diluted with methylene chloride (200 ml) and then washed first with saturated sodium bicarbonate (3 x 100 ml) and then with water. After drying over sodium sulfate, the solution is evaporated and the product is chromatographed to give 4.6 g of the desired alcohol (77% yield) as a thick oil. The molecular weight of the product is 332, 5 grams.

Example 26

Preparation of 1- / 3- (3- (4-chlorophenyl) -3-acetoxyproyl) phenyl / -3,3-dimethylurea

According to this example, a solution of the compound obtained in Example 25 in an amount

1.5 g, corresponding to 0.005 mol, acetic anhydride (1 ml) and triethylamime (1 ml) in methylene chloride (50 ml) were heated at reflux for 5 hours. The solvents are then evaporated and the residue is then chromatographed to give 0.9 g of the desired acetate (corresponding to 48% yield) as a thick oil. The molecular weight of this product is 374.5 »

Example 27

Preparation of 1-methyl-1- [3- (3- (4-chlorophenyl) -3-methoxypropyl) phenyl] 33,3-dimethylurea.

A solution of the compound of Example 25 (1.66 g, 0.005 mol) in tetrahydrofuran (60 ml) was cooled in an ice bath prior to the addition of sodium hydride as a 50% dispersion of 0.56 g. Stirring is continued for 5 minutes and methyl iodide (0.73 g) is added and the solution is allowed to warm to room temperature. Stirring is continued for 3 hours, then the reaction is quenched with 10% aq. hydrochloric acid solution, the product obtained was extracted into diethyl ether, washed with saturated sodium bicarbonate solution and water, and then dried and evaporated. The product was purified by chromatography to give 1.53 g of the desired product, corresponding to a yield of 55%. Mp 121-122 ° C.

Example 28

Preparation of 1- [3- (3- [4 * Chlorophenyl] -3-methylsulfonyloxypropyl) -3,3-dimethylurea.

In this example, a solution of the compound obtained in Example 25, in an amount

1.5 g, corresponding to 0.0047 mol, of 2 ml of methyl chloride and 1 ml of triethylamine in 50 ml of methylene chloride, heated at reflux for 1 hour. 0.9 g of the desired methyl sulfonate is obtained, corresponding to a yield of 47%. The molecular weight of this product is 410.5 ·

Example 1 a d у 29 to 97

Other compounds of formula (X) are prepared in an analogous manner to those described in Examples 23-28. Details are given in Table II below.

Example No. Аг А В X Ϊ R R Position Melting point Molecules, mass

В (vzhledem (° G) GO GO ГО 04 СП ГО

ro O © 04 / m oo © O 04 / ω O © © © ro w- © · - ro O ro what · * © F* 04 / O 1 1 1 1 1 1 ТЭ ТЭ 1 00 1 1 1 1 ₽— 1 04 / 00 ro r * тГ Ф 0) oo 1 © what 1 —- © © ro E- © «- ro r-4 z— ♦ ro oo · - what 04 / © - * - * - · - O O 1 1 · - 00 - 04 /

4-Methylphenyl-CO-H-CH 2 m 128-130

& φ & ф r4 r4 гЧ гЧ гЧ Оч 4ч »-Ч >> > » χ WITH >> L, h Ь C C с G С О О С Ф Ф φ Ф ф гЧ гЧ ф 4ч 4ч <u 4ч 4ч © © 4ч AND-. G О О O O о О О • č • гЧ О r4 r-4 гЧ гЧ гЧ ТЭ тз гЧ гЧ гЧ Н Н гЧ гЧ гЧ г-1 © © © © © 1 1 > » > » >> > » > » > » >> © O O О О υ а С С а а С а О 1 1 1 ω Ф Ф Ф ф ф ф ф F rt m 4ч 4ч 4ч 4ч 4ч 4ч <* ч 4ч

Table II (continued)

EXAMPLE NO. Аг А В Ϊ ^{R 1} X ^R Position ^T emperature molecule. mass

B melting (° C)

CM rA to LA γα

C- - θ ' vo OJ rt n- lA O C- Γ- O r— M · t vo an rf AI and* Γ- O O σ » WHAT OO 1 1 •O T3 1 ΟΟ 1 and\ ao t AND t AND t 1 AND AND la LA Φ φ cn 1 r— 1 rf · ov O CM LA rA OJ m O ai <—1 rH O lA m and" with* O FROM rT Φ and> CA oo AJ - 1 O O · - OO - oo C- * - · - * - -

eee a

Ft e

<* A fn YA γα YA CA oo ca YA OO YA oo oo X X X X X X X X X X X X X O O Q AT O at at O O O at at at

rAmm 'XXX

O UQ rl X O

γα m

32

CJ U X X

XXX

XXX X

X

X

X

X

X

X

X

X

X

X

X

X

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Example 97

Herbicidal activity.

In order to assess the herbicidal activity of the compounds of the present invention, these compounds were tested on a representative range of plants including: maize, Zea Mays (Hz), rice, Oryza sativa (R), corn leg slaughter, Echinochloa erusgalli (BG), oats , Avena sativa (0), linseed, Linum usitatissium (L), mustard, Sinapsis alba (M), sugar beet, Beta vulgaris (SB), and soy, Glycine max (S).

The tests can be divided into two categories, pre-emergence and post-emergence. In the pre-emergence tests, liquid formulations containing the compounds of the present invention were sprayed onto soils into which the seeds of the plant species mentioned above were sown. Two types of tests were carried out in post-emergence tests, namely soil wetting and foliage spraying. In soil wetting tests, soil in which plants of the above plant species were planted was moistened with liquid compositions containing the compounds of the present invention, and in tests in which were conducted on the foliage spraying, the seedlings were _C abovementioned plants sprayed with the above mentioned compositions according to the invention ·

The soil used in the above tests was treated horticultural soil ·

The formulations used in the above embodiments were those prepared by diluting with water solutions of test compounds in acetone containing 0.4% by weight of alkylphenol-ethylene oxide condensate, which is available under the trade designation TRITON X-155. Acetone solutions were diluted with water and the resulting compositions were applied at doses equivalent to 5 kilograms and / nobo 1 kilogram of active ingredient per hectare, in a volume equivalent of 600 liters per hectare, in soil spraying and foliage spraying tests and in batches. equivalent to 10 kilograms of active substance per hectare in a volume equivalent of 3 000 liters per hectare for soil moisturization tests ·

For pre-emergence tests, untreated soils used for plant cultivation were used for control and untreated soils in which plant seedlings were placed for post-emergence tests.

The herbicidal effect of test compounds was estimated visually on the twelfth day after spraying on foliage and soil, and on the thirteenth day after soil moisturization, the herbicidal effect was evaluated on a scale of 0 to 9 · Evaluation 0 means growth as untreated control plants and evaluation 9 means destruction. A shift of 1 unit in this linear row means an approximately 10% increase in effect level ·

The results obtained are shown in Table III below for these tests.

Table III (continued)

Soil moistening compound (10 kg / ha) of Example No. M 2 R BG OLU SB S

Table XII (continued)

Soil moistening compound (10 kg / ha)

Example # Mz R BG 0 L M SB with 27 Mar: 0 0 0 0 0 0 0 0

Table III Compound Dosing Spraying on foliage Preemergent application according to amount Example no. (kg / ha) Mz R BG 0 L M SB S Mz R BG 0 L M SB

23 5 0 0 0 0 4 7 3 0 0 0 0 0 0 0 0 0 1 0 0 0 0 3 6 0 0 0 0 0 0 0 0 0 0 24 5 0 0 0 0 0 3 9 0 1 0 0 3 0 4 8 9 4 0 0 0 0 0 1 9 0 25 5 0 0 0 0 4 8 9 4 0 0 0 0 0 5 8 0 1 0 0 0 0 4 7 9 3 0 0 0 0 0 0 7 0 26 5 0 0 0 0 0 - 9 - 1 0 0 0 4 7 9 4 4 0 0 0 0 0 - 7 - 27 Mar: 5 4 0 4 5 9 9 9 6 0 0 0 0 0 - 4 - 1 3 0 4 5 8 7 8 4 0 0 0 0 0 - 0 -

Table IXX (continued)

Soil moistening compound (10 kg / ha)

Example no. Mz R BG 0 L M SB with 28 0 0 0 0 0 3 9 2 29 0 0 0 0 0 0 6 0 30 0 0 0 2 3 4 9 0 31 0 0 0 0 0 0 0 0

Table XXI (continued)

Example Compound No.

Dosing rate (kg / ha)

Spraying on foliage

Ms R BG 0 L M SB S

Pre-emergence applications

Mz R BG O M M SB S

00007994

0007994

0 0 0 0

Table III (continued) Compound Dosing Spraying on foliage Pre-emergence applications according to quantity example no » (kg / ha) Mz R BGOLMSBS MzRBGOLMSBS

29 5 0 0 0 0 2 6 7 4 0 0 0 0 0 0 7 0 1 0 0 0 0 2 6 6 0 0 0 0 0 0 0 6 0 30 5 0 0 0 0 2 8 9 0 1 2 0 4 3 8 8 9 4 0 0 0 0 0 5 7 0 31 5 0 0 0 0 0 7 9 0 1 0 0 2 0 8 9 9 4 0 0 0 0 0 0 2 0

Table III (continued)

Compound of Example C. XHumidification of soil (10 kg / ha) Mz R ВО 0 L M SB WITH 32 0 0 0 0 0 3 4 3 33 0 0 0 0 0 7 0 0 34 0 0 0 0 0 3 3 0 35 0 0 0 0 0 7 4 0

Table III (continued) Compound Dosing Spraying on foliage Pre-emergence applications according to amount Mz R ВО 0 L M SB S MzR ВО 0 L M SB S Example no. (kg / ha)

32 1 4 3 7 5 9 9 9 6 0 0 5 4 0 4 9 3 33  - 1 0 0 5 3 6 7 9 5 0 0 0 0 0 0 7 0

- - ------ 1 2 0638994 0000278 0

- ........ ........

2 0758997 00004790

Table III (continued)

Soil moistening compound Ц0 ty / ha)

·· no. Mz R BG · L M SB WITH 36 0 0 0 0 0 0 0 0 37 - - - - - - - - 38 0 6 0 7 8 9 9 7 39 0 3 2 5 0 3 8 4

Table III (continued)

Compound Batch Sprayed on Foliage Pre-emergence Application according to Example No. mildness (kg / ha) Mz RBOLMSBS MzRBOLMSBS

385

2525896 00000300

234058 0

00 2025 0

25 23884 0 00 0000 0

Table III (continuation)

Soil moistening compound (10 kg / ha)

Example no. MZ R BG 0 L M SB WITH 40 - - - - - - - - 41 - - - - - - - - 42 2 8 3 5 6 9 9 6 43 0 8 2 6 5 8 8 5

Tatailka III (continued)

Compound Dosage Leaf Spray Preemmgent application according to Example No. 10

(kg / ha) M R O L M SB WITH M R (B) 0 L M SB WITH 40 - 1 1 3 7 6 9 9 9 7 0 0 0 0 0 7 8 0 41 1 5 8 6 9 9 9 6 0 0 0 0 0 0 0 0 0

Table III (continued)

Example Compound No.

Dosing rate (kg / ha)

Spraying on the cistern

Preemmegenic applications

Ms R BG 0 L M SBS Ms R BG 0 L M SBS

Table III (continued)

Soil moistening compound (10 kg / ha)

Example no. Mz R BG 0 L M SB WITH 44 0 0 0 0 2 0 3 2 45 0 0 5 2 0 7 9 1 46 3 0 2 0 0 8 0 3 47 0 2 4 0 0 9 7 2

Table III (continued)

Compound Dosage Spraying on Isiox Pre-marketing Application according to Example No. Qty

(kg / ha) Mz R BG 0 L M SB WITH Mz R BG 0 L M SB WITH 44 5 0 0 0 2 0 2 6 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 2 2 0 0 0 0 0 0 0 0 0 45 5 2 1 8 0 9 9 9 6 0 0 O 0 0 8 9 1 1 0 0 8 0 8 9 9 6 0 0 0 0 0 6 8 0 46 5 0 0 0 0 0 9 2 3 0 0 0 0 0 4 4 0 1 0 0 0 0 0 9 2 0 0 0 0 0 0 0 0 0 47 5 0 0 5 0 2 9 9 6 0 0 0 0 0 6 8 0 1 0 0 4 0 0 9 6 5 0 0 0 0 0 0 3 0

Table III (continued)

Soil moistening (10 kg / ha)

Compound of

Example no. Mz R BG 0 L M SB WITH 48 0 2 3 2 2 9 9 4 49 0 0 0 0 0 9 9 3 50 0 4 0 5 0 9 7 6 51 0 0 0 0 0 0 0 0

Table III (continued)

Compound according to Dosage Spraying to a Mixed Primer Example No.

(kg / ha) Mz R BG O L M SB WITH Mz R BG 0 L M SB WITH 48 5 0 0 7 0 9 9 9 6> 0 0 0 0 0 8 8 2 ¹ 0 0 5 0 8 9 9 5 0 0 0 0 0 2 0 0 49 5 0 0 5 0 5 9 9 7 0 0 0 0 0 1 9 0 1 0 0 5 0 0 9 9 6 0 0 0 0 0 0 2 0 50 5 0 0 0 0 2 9 7 5 0 0 0 0 3 4 6 0 1 0 0 0 0 0 0 2 0 51 - 1 0 0 5 0 0 9 9 4 0 0 0 0 0 0 0 0

Table III (continued)

The compound according to the humidifier !! soil (10 kg / ha)

Example no. Hz R BG O L M SB WITH 52 0 0 0 0 0 2 4 0 53 0 0 0 3 2 9 3 3 54 0 8 6 3 4 9 9 5 55 0 0 0 0 0 0 0 0

factory III (continued)

Dosage Compound Compound for the ovíι ^ ηΜτ ^ θη ^ ί application of Example No.

(kg / ha) Mz R BG O L M SB WITH M R BG O L M sb '; 52 - 1 3 0 8 4 6 9 9 6 0 0 0 0 0 2 6 2 53 5 4 5 9 0 5 9 8 6 0 0 0 0 0 0 0 0 1 0 0 2 0 0 9 3 2 0 0 0 0 0 0 0 0 54 5 4 5 9 5 6 9 9 6 0 0 0 0 0 7 9 0 1 0 0 7 0 4 9 9 5 0 0 0 0 0 2 3 0 55 5 0 0 8 3 2 9 9 4 0 0 0 0 0 3 7 0 1 0 0 6 0 0 9 9 4 0 0 0 0 0 0 2 0

Table III (continued)

Soil moistening compound (10 kg / ha)

Example no. Mz R BG 0 L M SB WITH 56 0 2 3 4 3 9 9 5 57 0 2 5 5 9 9 9 4 58 0 0 0 0 0 0 0 0 59 0 4 6 2 5 5 9 9

Table III (continued)

Batch Spray Compound Preemergence Application of Example No. Quantity

(kg / ha) Mb R BG 0 L M SB WITH Mb R BG 0 L M SB WITH 56 5 0 3 8 0 3 9 9 5 0 0 0 0 0 3 7 0 1 0 0 8 0 0 9 9 4 0 0 0 0 0 0 2 0 57 5 4 5 9 6 8 9 9 8 0 0 3 3 2 8 8 3 1 3 3 9 6 8 9 9 7 0 0 2 2 0 6 8 2 58 5 0 0 8 3 4 9 9 5 0 0 0 0 0 0 0 0 1 0 0 3 0 0 7 0 3 0 0 0 0 0 0 0 0 59 5 5 6 9 6 8 9 9 8 0 0 3 3 4 7 6 0 1 3 5 8 5 8 9 9 8 • 0 0 0 0 0 6 5 0

Table III (continued)

Soil moistening compound (10 kg / ha)

příklsdu č. Mb R BG 0 L M SB WITH 60 0 0 4 0 3 7 0 4 61 0 0 4 2 3 5 3 2 62 0 0 0 0 0 3 7 3 63 0 0 0 0 0 0 3 0

Table III (continued)

Metered Compound Foliage Spray Preemergence Applications

Example no. quantity (kg / ha) Mz R BG 60 5 2 3 8 1 1 2 8 61 5 3 4 8 1 2 2 7 62 5 5 6 9 1 2 4 8 63 5 2 3 9 1 0 0 7

0 L M SB WITH Mz R BG 0 L at SB WITH 6 8 9 9 7 0 0 0 0 0 7 8 0 6 6 9 9 5 0 0 0 0 0 4 4 0 6 7 9 9 7 0 0 0 0 0 7 8 0 4 6 9 9 7 0 0 0 0 0 3 3 0 7 9 9 9 9 0 0 0 0 3 8 9 3 7 8 9 9 7 0 0 0 0 0 6 7 0 6 8 9 9 8 0 0 0 0 2 8 8 0 6 8 8 9 7 0 0 0 0 0 4 7 0

Table III (continued)

Soil Moisture Compound (10 kg / ha)

Example no. Mz R BG 0 L M SB WITH 64 0 0 0 4 4 4 9 0 65 0 0 0 0 0 0 0 0 32 + 64 0 0 0 0 3 9 6 0 66 + 67 0 0 0 0 0 0 0 0

Table III (continued)

Compound according to Metered Foliage Pre-emergence Application of Example No. 2

(kg / ha) Mz R BG 0 L M SB WITH líz R BG 0 L M SB S 64 5 3 2 9 6 9 9 9 5 0 0 0 0 3 6 7 3 1 2 0 8 5 8 9 9 3 0 0 0 0 0 4 5 0 65 5 2 0 8 4 7 9 9 4 0 0 0 0 2 5 5 0 1 2 0 8 4 4 8 7 4 0 0 0 0 0 3 2 0 32 ♦ 64 5 4 2 9 7 9 9 9 7 0 0 0 0 0 7 8 0 1 2 0 8 5 8 9 9 6 0 0 0 0 0 5 7 0 66 + 67 5 2 0 8 6 7 8 9 4 0 0 0 0 0 0 0 0 1 0 0 7 3 2 7 7 2 0 0 0 0 0 0 0 0

X

Table III (continued)

Soil Moisture Compound (10 kg / ha) of Example No. Mz ♦ 69C ♦ 710

Ч 730 ♦ 750

R BG 0 L M SB with 0 0 0 0 5 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Table XII (continued)

Dosing Compound Foliage Preemergence Applications

of Example 6. quantity (kg / ha) Mz R BG 68 * 69 5 3 2 8 1 3 0 8 70 ♦ 71 5 3 0 8 1 2 0 7 72 * 73 5 3 0 8 3 1 0 7 74 * 75 5 3 0 8 1 2 0 7

0 L M SB WITH Mz R BG 0 L M SB WITH 6 8 9 9 5 0 0 0 0 0 8 8 0 3 6 9 9 4 0 0 0 0 0 5 6 0 5 7 9 9 3 0 0 0 0 0 4 4 0 3 4 7 3 2 0 0 0 0 0 0 0 0 4 5 9 9 4 0 0 0 0 0 5 6 0 0 4 8 6 0 0 0 0 0 0 2 2 0 4 8 9 9 4 0 0 0 0 0 5 5 0 0 4 8 8 1 0 0 0 0 0 2 1 0

Table XXX (continued)

Compound according to Soil Moisture (10kg / ha) of Example No. MzRBGOLMSBS

Table III (continued)

Example Compound ·

Dosage Spraying on Foliage Pre-emergence application rate (kg / ha) Mz R BG OLMSBS MzRBGOLMSBS + 77

O

* 79

o + 82

0 05 05873 00000350

Table III (continued)

Soil moistening compound (10kg / ha)

Example no. Mz R BG 0 L M SB WITH 83 * 84 0 0 0 0 0 0 0 . 0 85 + 86 0 0 0 0 0 0 0 0 87 * 88 0 0 0 0 0 0 0 0 89 * 90 0 0 0 0 0 0 0 0

Table III (continued)

Dosage Compound Foliage Pre-emergence Application of Example No. Quantity (kg / ha) MzRBGOLMSBS MzRBGOLMSBS

84 * 83 - 1 0 0 0 0 5 8 7 2 0 0 0 0 0 0 0 0 85 ♦ 86 5 0 0 7 3 6 9 9 3 0 0 0 0 0 4 0 0 1 0 0 0 0 3 7 2 1 0 0 0 0 0 0 0 0 87 ♦ 68 5 0 0 7 3 8 9 9 4 0 0 4 2 0 7 9 5 1 0 0 3 0 3 9 8 2 0 0 0 0 0 3 0 0 89 ♦ 90 5 4 2 8 5 9 9 9 8 0 0 0 0 0 8 9 2 1 4 2 7 5 9 9 9 5 0 0 0 0 0 and 2 2

Table III (continued)

Example Compound No. Soil moistening (10 kg / ha) MZ R BG 0 L M SB with 91 0 0 0 0 0 0 0 0 • 92 0 0 0 0 0 0 0 0 - 93 0 0 0 0 0 0 0 0 94 0 0 0 0 0 0 0 0

Table III (continued)

Dosage Spray Compound 1 is a pre-emergence application of Example No. 1

(kg / ha) Mz R BG 0 L M SB WITH Mz R BG 0 L M SB 91 3 1 0 0 0 0 3 8 1 0 0 0 0 0 0 0 0 92 5 3 0 8 2 4. 8 8 7 0 0 0 0 0 0 0 1 2 0 7 2 0 7 8 6 0 0 0 0 0 0 0 93 5 2 3 8 6 7 9 9 5 0 0 0 0 0 0 0 1 0 0 4 2 3 5 3 3 0 0 0 0 0 0 0 94 5 0 0 7 0 5 9 9 5 0 0 0 0 0 0 0 1 0 0 0 0 2 5 5 3 0 0 0 0 0 0

Table III (continued)

Compound according to Moisture Soil (10 kg / ha) of Example No. M 2 R BG O, I> M SB S

2 0 0 0 0 0 0 0

00250450

Tobacco III (continued)

Compound of Dosing Spray ca iSao Pretmergent applications Example no. mюSsW ^(k g _< / ^h a ⁾ MzRBJOLMBS Mte R BG, OLMBS

5 42728997 00000000

20306994 00000000

- ................

03063764 03532342 example 98

Fuming efficiency.

(a) Efficacy against virulent powdery mildew (Plamo para viticola, Pra).

This test was performed as a direct antisporant test in which foliage was sprayed. The lower surfaces of the inhaled leaves of vine shrubs were inoculated by spraying with an aqueous suspension containing 10? zoosppoeanium per milliliter 2 days before treatment with the test compound. These inoculated plants were then kept for 24 hours in a high humidity environment and then for 24 hours at greenhouse ambient temperature and humidity. Thereafter, these plants were dried and the infected leaves were separated and sprayed on the lower surfaces with a 1: 1 solution of the active ingredient in water / acetone containing 0.04% Triton X-155 (commercial designation). This spraying was carried out with the aid of a shifting sprayer, with an effective load of 620 l / ba and the active compound concentration calculated to apply from 1 kg / ha. Along the axis (a), the agrimony leaves of the sprayed leaves were immersed in water and the leaves were then reinserted in a high humidity environment for another 966 hour incubation, followed by analysis. Evaluation of fungicidal efficacy was performed by estimating the area covered by sponge in percent and comparing it with the results of the control castings.

b) Un &lt; n &lt; o &gt; against the paddy (Plasmopara viticola, Prt).

This test was performed as a translaminar protection test using foliar spraying. The top surfaces of the vine leaves were sprayed with a dose of 1 kioogam of active ingredient per hectare using a shifting sprayer. The lower surfaces of 1 ± at were then inoculated at intervals of up to 6 hours. after treatment with the SKU ^ ^ Nina nstfikem aqueous suspension obseduj ^ i ¹ 0? zoovpopvrg ^í í / ^m ilitr me. The inoculated plants were then maintained for 24 hours in a high humidity environment, 4 days at greenhouse ambient temperature and humidity, and were then transferred to a high humidity environment for 24 hours. Evaluation of fungicide! The efficacy was to compare the percentage of leaf area that was polluted by the spore with the leaf area.

(c) Activity against paddy in barley (Erysiphe grarninis, Eg).

Й51 this es ^{t t} was determined by saying шlt ^{p i} with ^p vrU.aítíí effectiveness composites ^p ^ (Hc ⁱⁿ ynal ^ez on which were applied as a foliar poosřik. For each compound about 40 rearward grown barley seedling stage to form one 24 hours after inoculation, the seedlings were sprayed with a solution of the compound as a mixture with acetone (50%, a surfactant (0)), in a plastic container in a sterile compost intended for flower pots. , 04%) and water, using a shifting sprayer as in embodiment a) The applied rate corresponded to 1 kilogrm of active substance per hectare, the first estimation of the plant infestation was made 5 days after treatment, with the total extent of savings of treated plants compared to boiler plants ..

d) Efficacy against paddi in apples (Bodoophaera leicotrica, P. ·).

This test was performed as a direct non-spontaneous test, using only spray on the foliage. Porvchy top of the apple seedling leaves were sprayed with aqueous suspensions invkulvvány ^í í ^which otaahovala 1 ^0? k ^ ii ^ mn to ITRs which prov ^{e b} t was Deno ^{BC 2} days before the test compound-examination procedure. The seeded plants were immediately dried and then kept at a greenhouse temperature of okU and humidity prior to treatment. The plants were then sprayed with the active ingredient, applied at a rate of 1 kilogram of active ingredient per hectare, and a shifting sprayer. After drying, the plants were again placed in a room with high temperature and humidity and maintained in the room for up to 9 days, followed by an evaluation of the fungicidal efficacy. Evaluation of fungicidal efficacy was performed by comparing the percentage of leaf area covered by sporulation and that of the control leaves.

(e) Activity against powdery mildew in barley (Erysiphe graminis, Ega).

In this test, the systemic protective efficacy of the compounds of the invention applied as soil moisturizer was determined. For each compound, the soil was moistened with a dose corresponding to 10 kilograms per hectare. About 25 barley seeds, Golden Promiae, were placed in the upper layer of treated soil and covered with a layer of 1 cm of untreated soil. After 5 days, the extent of sporulation was compared to control plants.

(f) Effect on cez in bean (Uromyces fabae, Uf).

*

In this test, the translaminar antisporulant and the activity of the compounds of the present invention, which were applied as a foliage spray, were examined. For each compound, bean seedlings with two pairs of leaves were inoculated with an aqueous suspension containing 10 * spores per milliliter. This is done by comparing the relative density of sporulating vesicles with the control plants.

The extent of disease control achieved in these tests is expressed in Table IV below as an estimate of this control, with greater than 80% disease control being reported as classification 2 after the test and disease control ranging from 50% to 80% is reported as classification 1 after the test.

Teams with more than 50% overnight control achieved

Table IV

Example Compound No.

23 Pva (2) 25 Pva (2) 26 Uf (1) 27 Mar: Pva (1) 32 Eg (2); PI (1) 33 Uf (1) 34 Pra (1); Eg (1) 35 Pva (2); Eg (1) 37 Pva (s) 38 Ega (2) J U (2) 39 Uf (1) 40 Pva (1); Pvt (2); Ega (1) 41 Pva (2); Pvt (2); Eg (1) 42 Pva (1); Ega (2) 43 Pva (1) 45 Pva- (1); Eg (2); Uf (1) 47 Uf (1) 49 U ^ (2) 50 Uf (1) 51 Pva (1); Pvt (1); Uf (1) 52 Pva (1); Prt (2) 56 Pva (2) 57 Pva (2) 59 P »t (1) is Eg (1) 5 PL (1) 5 1 60 Uf (1) 61 Uf (1) 62 Pvt (1); Eg (1) 63 Pvt (1); Eg O); Uf (1) 68 + 69 'Eg (2) 78 ♦ 79 Pv (2) j Eg (2) 80 Uf (1). 81 * 82 W (1) 91 Uf (1) 93 Pva (2), 95 Pvt (2)

Claims (3)

SUBJECT OF THE INVENTION 1. A herbicidal e / or funicidní means indicating the ttCm that comprises as active ingredient of the formula I frnylmočovCnu KDR (and R ₂ independently represent hydrogen or methyl, X said atom guided ,, Y stands for hydrogen or CKLora, A 0 represents a rzoidyl group or a phenyl group optionally substituted by a chlorine or fluorine atom, a methyl group, a trifluoromethyl group or an oetho group. one of A and B is * CO, = CH (OR 4) or = CH (R 5), wherein R) represents a hydrogen atom, a C 1 -C 4 alkyl group, a phenyl group, a benzyl group or an alkanoyl or alkylsulfonyl group in which the alkyl moiety contains 1 to 4 carbon atoms, or represents a group of formula> C 1 R 1r (ORr) or> C (SR) (SRr), wherein the two R 1 groups taken together represent an alkylene group containing up to 4 carbon atoms, and. the other of A and B being an ethylene group, a 1,2-erythyethylode group, a vinylene group or a 1,2-cyclopbtrylene group, together with a carrier. 2. A composition according to claim 1, wherein the active ingredient is a compound of formula (I) wherein both R and R2 are methyl, Ar is phenyl, which is: optionally substituted with a chlorine or fluorine atom; It represents a hydrogen atom, a thiol, ethyl or Csopboryl group, a benzyl group, an aryl group or a mercurylphenyl group, R 1 represents an ethylene group and the other substituents have the meaning given in point 1. 3. A composition according to claim 2, wherein the active ingredient is a compound of formula (I) wherein one of the substituents A and B represents a group of the formula: